Derivatives of 4‐(2‐hydro­xy­lphenyl)‐2‐phenyl‐2,3‐di­hydro‐1,5‐benzothiazepine

In the structures of 2‐(4‐chloro­phenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₁H₁₆ClNOS, 4‐(2‐hy­droxy­phenyl)‐2‐(4‐tolyl)‐2,3‐di­hydro‐1,5‐ben­zo­thia­zepine, C₂₂H₁₉NOS, and 4‐(2‐hydroxyphenyl)‐2‐(3‐methoxy­phenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₂H₁₉NO₂S, the central seven‐membered heterocyclic rings adopt twist‐boat conformations in which the N atoms are involved in strong intramolecular hydrogen bonds with the hydroxyl H atoms, resulting in six‐membered rings.     

rac‐5‐Diphenylacetyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine and rac‐5‐formyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine

rac‐5‐Diphenylacetyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine, C₂₆H₂₇NOS, (I), and rac‐5‐formyl‐2,2,4‐trimethyl‐2,3,4,5‐tetrahydro‐1,5‐benzothiazepine, C₁₃H₁₇NOS, (II), are both characterized by a planar configuration around the heterocyclic N atom. In contrast with the chair conformation of the parent benzothiazepine, which has no substituents at the heterocyclic N atom, the seven‐membered ring adopts a boat conformation in (I) and a conformation intermediate between boat and twist‐boat in (II). The molecules lack a symmetry plane, indicating distortions from the perfect boat or twist‐boat conformations. The supramolecular architectures are significantly different, depending in (I) on C—H...O interactions and intermolecular S...S contacts, and in (II) on a single aromatic π–π stacking interaction.     

A Novel Reaction of 1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) or 1,5‐Diazabicyclo[4.3.0]non‐5‐ene (DBN) with Benzyl Halides in the Presence of Water

1,8‐Diazabicyclo[5.4.0]undec‐7‐ene (DBU) reacted with benzyl halides in CH₂Cl₂/H₂O 1 : 1 (v/v) to afford a mixture of eleven‐membered cyclic amide 1 and seven‐membered cyclic amide 2 . When the reaction was carried out in EtOH/H₂O 1 : 1 (v/v), product 2 was obtained as the major product. 1,5‐Diazabicyclo[4.3.0]non‐5‐ene (DBN) gave the five‐membered cyclic amide 3 as the sole product under the same reaction conditions.     

N,N′‐Bis(2‐hydroxybenzylidene)pentane‐1,5‐diamine

In the title potential O,N,N′,O′‐tetradentate Schiff base ligand {systematic name: 2,2′‐[pentane‐1,5‐diylbis(nitrilomethylidyne)]diphenol}, C₁₉H₂₂N₂O₂, the mutual orientation of the three planar fragments determines the conformation of the molecule. The dihedral angles between the planes of the two salicylidene groups and the plane of the central extended pentane chain are 78.4 (2) and 62.0 (3)°, and the angle between the terminal ring planes is 55.4 (1)°. Strong intramolecular O—H...N hydrogen bonds close almost‐planar six‐membered rings, and the O—H bonds are elongated as a result of hydrogen‐bond formation.     

4‐(2‐Hydroxyphenyl)‐2‐phenyl‐2,3‐dihydro‐1H‐1,5‐benzodiazepine and the 2‐(2,3‐dimethoxyphenyl)‐, 2‐(3,4‐dimethoxyphenyl)‐ and 2‐(2,5‐dimethoxyphenyl)‐substituted derivatives

The 1,5‐benzodiazepine ring system exhibits a puckered boat‐like conformation for all four title compounds [4‐(2‐hydroxyphenyl)‐2‐phenyl‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₁H₁₈N₂O, (I), 2‐(2,3‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (II), 2‐(3,4‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (III), and 2‐(2,5‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (IV)]. The stereochemical correlation of the two C₆ aromatic groups with respect to the benzodiazepine ring system is pseudo‐equatorial–equatorial for compounds (I) (the phenyl group), (II) (the 2,3‐dimethoxyphenyl group) and (III) (the 3,4‐dimethoxyphenyl group), while for (IV) (the 2,5‐dimethoxyphenyl group) the system is pseudo‐axial–equatorial. An intramolecular hydrogen bond between the hydroxyl OH group and a benzodiazepine N atom is present for all four compounds and defines a six‐membered ring, whose geometry is constant across the series. Although the molecular structures are similar, the supramolecular packing is different; compounds (I) and (IV) form chains, while (II) forms dimeric units and (III) displays a layered structure. The packing seems to depend on at least two factors: (i) the nature of the atoms defining the hydrogen bond and (ii) the number of intermolecular interactions of the types O—H...O, N—H...O, N—H...π(arene) or C—H...π(arene).     

The crystal structure of 9‐chloro‐4,5‐dihydro‐2‐ethyl‐1‐(2,4,6‐trichlorophenyl)‐1H‐1,2,4‐triazolo[3,2‐d][1,5]‐benzoxazepinium hexachloroantimonate

The title compound 4 , i.e. 9‐chloro‐4,5‐dihydro‐2‐ethyl‐1‐(2,4,6‐trichlorophenyl)‐1H‐1,2,4‐triazolo[3,2‐d]‐[1,5]benzoxazepinium hexachloroantimonate, is a novel 6‐7‐5 tricyclic heterocycle. C₁₈H₁₄Cl₄N₃O·SbCJ₆, M = 764.61, P2₁/c(#14), a = 13.457(4), b = 11.583(2), c = 18.992(3) Å α = 90, β = 110.11(1)°, Z = 4, V = 2780(1) ų, D_c = 1.827 g/cc, μ (MoKα) = 19.69 cm^?1, F(000) = 1488.00, T = 293 K, R_int = 0.055 for 3094 independent reflections with I>3.00σ(I). The five‐membered heterocyclic ring is nearly planar, with the trichlorophenyl ring at N(2) almost perpendicular to it. However, the seven‐membered ring is not planar, but adopts a twist‐boat conformation.     

由邻苯二胺合成苯并咪唑、喹喔啉以及1-H-2,3－二氢1,5-苯并氮杂卓

A series of benzo-fused heteroaromatic compounds with 5-, 6- and 7-membered tings, such as benzimidazole,quinoxaline and 1H-1,5-benzodiazepine derivatives, were synthesized through condensation reaction of o-pheny1-enediamine with ary1 aldehydes or ketones. The experimental conditions were carefully examined, and the products were characterized by ^1H NMR, ^13C NMR, MS, IR and elemental analyses. In addition, the structure of a benzodiazaepine derivative with 7-membered ring was confirmed by single crystal X-ray diffraction analysis.     

Three 4,7‐diaryl‐2‐ethylsulfanylpyrazolo[1,5‐a][1,3,5]triazines

The molecular dimensions of 2‐ethylsulfanyl‐7‐(4‐methylphenyl)‐4‐phenylpyrazolo[1,5‐a][1,3,5]triazine, C₂₀H₁₈N₄S, (I), 7‐(4‐chlorophenyl)‐2‐ethylsulfanyl‐4‐phenylpyrazolo[1,5‐a][1,3,5]triazine, C₁₉H₁₅ClN₄S, (II), and 4,7‐bis(4‐chlorophenyl)‐2‐(ethylsulfanyl)pyrazolo[1,5‐a][1,3,5]triazine, C₁₉H₁₄Cl₂N₄S, (III), show evidence for some aromatic delocalization in the pyrazole rings. The conformations adopted by the ethylsulfanyl substituents are different in all three compounds. There are no hydrogen bonds in any of the crystal structures, but pairs of molecules in (II) and (III) are linked into centrosymmetric dimers by π‐stacking interactions.     

Synthesis of 1,3,4‐Oxadiazole Acyclo C‐Nucleosides Bearing 5‐Methylthio{7‐substituted‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐yl}moieties

Oxidative cyclization of the sugar hydrazones ( 3_a‐f ) derived from {7H‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐ylsulfanyl}acetic acid hydrazide ( 1 ) and aldopentoses 2_a‐c or aldohexoses 2_d‐f with bromine in acetic acid in the presence of anhydrous sodium acetate, followed by acetylation with acetic anhydride gave the corresponding 2‐(per‐O‐acetyl‐alditol‐l‐yl)‐5‐methylthio{7H‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐yl}‐1,3,4‐oxadiazoles ( 5_a‐f ). Condensative cyclization of the sugar hydrazones ( 3_a‐f ) by heating with acetic anhydride gave the corresponding 3‐acetyl‐2‐(per‐O‐acetyl‐alditol‐1‐yl)‐2,3‐dihydro‐5‐methylthio{7‐acetyl‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐yl}‐1,3,4‐oxadiazoles ( 11_a‐f ). De‐O‐acetylation of the acyclo C‐nucleoside peracetates ( 5 and 11 ) with methanolic ammonia afforded the hydrazono lactones ( 7 ) and the acyclo C‐nucleosides ( 12 ), respectively. The structures of new oxadiazole derivatives were confirmed by analytical and spectral data.     

A comparison of 2,7‐di­hydro‐2,2,7,7‐tetra­methyl‐3,6‐di­phenyl‐1,4,5‐thiadiazepine and the corresponding 1,1‐­dioxide

The structures of the highly substituted title heterocycles, C₂₀H₂₂N₂S and C₂₀H₂₂N₂O₂S, have been determined at 123 (1) K. Both mol­ecules possess exact C₂ symmetry and the seven‐membered rings have very similar twist‐boat conformations. The magnitudes of the C—S—C bond angles, 107.13 (6) and 108.27 (7)°, respectively, are influenced significantly by the four substituent methyl groups on the seven‐membered rings.     

1,5‐Dipolar Electrocyclizations of Thiocarbonyl Ylides Bearing CN Groups: Reactions of N‐[(Dimethylamino)methylene]thiobenzamide and 2‐(Dimethylhydrazono)‐1‐phenylethane‐1‐thione with Diazo Compounds

The reactions of thiobenzamide 8 with diazo compounds proceeded via reactive thiocarbonyl ylides as intermediates, which underwent either a 1,5‐dipolar electrocyclization to give the corresponding five membered heterocycles, i.e., 4‐amino‐4,5‐dihydro‐1,3‐thiazole derivatives (i.e., 10a, 10b, 10c , cis‐ 10d , and trans‐ 10d ) or a 1,3‐dipolar electrocyclization to give the corresponding thiiranes as intermediates, which underwent a S_Ni′‐like ring opening and subsequent 5‐exo‐trig cyclization to yield the isomeric 2‐amino‐2,5‐dihydro‐1,3‐thiazole derivatives (i.e., 11a, 11b, 11c , cis‐ 11d , and trans‐ 11d ). In general, isomer 10 was formed in higher yield than isomer 11 . In the case of the reaction of 8 with diazo(phenyl)methane ( 3d ), a mixture of two pairs of diastereoisomers was formed, of which two, namely cis‐ 10d and trans‐ 10d , could be isolated as pure compounds. The isomers cis‐ 11d and trans‐ 11d remained as a mixture. In the reactions of the thioxohydrazone 9 with diazo compounds 3b and 3d , the main products were the alkenes 18 and 23 , respectively. Their formation was rationalized by a 1,3‐dipolar electrocyclization of the corresponding thiocarbonyl ylide and subsequent desulfurization of the intermediate thiiran. As minor products, 2,5‐dihydro‐1,3‐thiazol‐5‐amines 21 and 24 were obtained, which have been formed by 1,5‐dipolar electrocyclization of the thiocarbonyl ylide, followed by a 1,3‐shift of the dimethylamino group.     

2,5‐Dimethyl‐6,7‐dihydrobenzo[h]pyrazolo[1,5‐a]quinazoline and 2‐tert‐butyl‐5‐methyl‐6,7‐dihydrobenzo[h]pyrazolo[1,5‐a]quinazoline

In both 2,5‐dimethyl‐6,7‐dihydrobenzo[h]pyrazolo[1,5‐a]quinazoline, C₁₆H₁₅N₃, (I), and 2‐tert‐butyl‐5‐methyl‐6,7‐dihydrobenzo[h]pyrazolo[1,5‐a]quinazoline, C₁₉H₂₁N₃, (II), which crystallizes with Z′ = 2 in the space group P, the non‐aromatic carbocyclic rings adopt screw‐boat conformations. The molecules of (I) are linked into chains of rings by a combination of C—H...N and C—H...π(arene) hydrogen bonds, while in (II) there are no hydrogen bonds of any kind.     

Asymmetric Ruthenium‐Catalyzed Hydrogenation of 2,6‐Disubstituted 1,5‐Naphthyridines: Access to Chiral 1,5‐Diaza‐cis‐Decalins

The first asymmetric hydrogenation (AH) of 2,6‐disubstituted and 2,3,6‐trisubstituted 1,5‐naphthyridines, catalyzed by chiral cationic ruthenium diamine complexes, has been developed. A wide range of 1,5‐naphthyridine derivatives were efficiently hydrogenated to give 1,2,3,4‐tetrahydro‐1,5‐naphthyridines with up to 99 % ee and full conversions. This facile and green protocol is applicable to the scaled‐up synthesis of optically pure 1,5‐diaza‐cis‐decalins, which have been used as rigid chelating diamine ligands for asymmetric synthesis.     

Synthesis and spectral properties of 2‐methylthio‐3H‐7‐[(o‐; m‐ and p‐substituted)phenoxy]‐4‐(p‐substituted‐phenyl)‐[1,5]benzodiazepines

A series of eleven new 2‐methylthio‐3H‐7‐[(o‐; m‐ and p‐substituted) phenoxy]‐4‐(p‐substituted‐phenyl)‐[1,5]benzodiazepines, which have potentially useful pharmacological activities, has been synthesized by condensing the 4‐[(o‐; m‐ and p‐R₁)phenoxy]‐1,2‐phenylendiamines with 3,3‐dimercapto‐1‐(p‐R₂‐phenyl)‐2‐propen‐1‐one. Afterward the lH‐[1,5]benzodiazepine‐2‐thiones obtained were treated with sodium hydride and methyl iodide. The structure of all products was corroborated by ir, ¹H nmr, ¹³C nmr and ms.     

Synthesis,Crystal Structures,and Fungicidal Activity of Novel 1,5‐Diaryl‐3‐(glucopyranosyloxy)‐1H‐pyrazoles

Five novel pyrazole‐coupled glucosides, 1,5‐diaryl‐1H‐pyrazol‐3‐yl 2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐glucopyranosides 5a – 5e , were synthesized by the phase‐transfer catalytic reaction of 1,5‐diaryl‐1H‐pyrazol‐3‐ols 4a – 4e with acetobromo‐α‐D ‐glucose in H₂O/CHCl₃ under alkaline conditions, using Bu₄N⁺Br^? as catalyst. Then, glucosides 5a – 5c were deacetylated in a solution of Na₂CO₃/MeOH to yield the 1,5‐diaryl‐3‐(β‐D ‐glucopyranosyloxy)‐1H‐pyrazoles 6a – 6c . Their structures were characterized by ¹H,¹H‐COSY, ¹H‐, ¹³C‐, and ¹⁹F‐NMR spectroscopy, as well as elemental analysis. The structures of 5d and 6c were also determined by single‐crystal X‐ray diffraction analysis. A preliminary in vitro bioassay indicated that compounds 4e and 5d exhibited excellent‐to‐medium fungicidal activity against Sclerotinia sclerotiorum at the dosage of 10 μg/ml.     

Two isomeric 2‐[4‐chloro‐2‐fluoro‐5‐(prop‐2‐ynyloxy)phenyl]hexahydro­isoindole‐1,3‐dione compounds

The molecular structures of 2‐[4‐chloro‐2‐fluoro‐5‐(prop‐2‐ynyloxy)phenyl]‐1,3,4,5,6,7‐hexahydro­isoindole‐1,3‐dione, C₁₇H₁₃ClFNO₃, (I), and the isomeric compound 2‐[4‐chloro‐2‐fluoro‐5‐(prop‐2‐ynyloxy)phenyl]‐cis‐1,3,3a,4,7,7a‐hexahydro­isoindole‐1,3‐dione, (II), are, as anticipated, significantly different in their conformations and in the distances between the farthest two atoms. The six‐membered ring of the 1,3,4,5,6,7‐hexahydro­isoindole‐1,3‐dione moiety in (I) adopts a half‐chair conformation. The dihedral angle between the five‐membered dione ring of (I) and the benzene ring is 50.96 (7)°. The six‐membered ring of the cis‐1,3,3a,4,7,7a‐hexahydro­isoindole‐1,3‐dione moiety in (II) adopts a boat conformation. The dihedral angle in (II) between the five‐membered dione ring and the benzene ring is 61.03 (13)°. In the crystal structures, the molecules are linked by C—H⋯O hydrogen bonds and weak π–π interactions. Compound (I) is a much more potent herbicide than (II). The Cl⋯H distances between the farthest two atoms in (I) and (II) are 11.37 and 9.97 Å, respectively.     

2,3:4,6‐Di‐O‐isopropylidene‐α‐l‐sorbofuranose and 2,3‐O‐isopropylidene‐α‐l‐sorbofuranose

In the title compounds, C₁₂H₂₀O₆, (I), and C₉H₁₆O₆, (II), the five‐membered furanose ring adopts a ⁴T₃ conformation and the five‐membered 1,3‐dioxolane ring adopts an E₃ conformation. The six‐membered 1,3‐dioxane ring in (I) adopts an almost ideal ^OC₃ conformation. The hydrogen‐bonding patterns for these compounds differ substantially: (I) features just one intramolecular O—H...O hydrogen bond [O...O = 2.933 (3) Å], whereas (II) exhibits, apart from the corresponding intramolecular O—H...O hydrogen bond [O...O = 2.7638 (13) Å], two intermolecular bonds of this type [O...O = 2.7708 (13) and 2.7730 (12) Å]. This study illustrates both the similarity between the conformations of furanose, 1,3‐dioxolane and 1,3‐dioxane rings in analogous isopropylidene‐substituted carbohydrate structures and the only negligible influence of the presence of a 1,3‐dioxane ring on the conformations of furanose and 1,3‐dioxolane rings. In addition, in comparison with reported analogs, replacement of the –CH₂OH group at the C1‐furanose position by another group can considerably affect the conformation of the 1,3‐dioxolane ring.     

Synthesis of Highly Functionalized γ‐Lactones via 1,5‐Electrocyclic Ring Closure

We have investigated 1,5‐electrocyclic ring‐closure reactions of conjugated esters with dimethyl diazomalonate in the presence of [Cu(acac)₂] as catalyst. Our new protocol offers an easy entry to various polyfunctionalized γ‐lactones in high yields. Their subsequent derivatives may be used as valuable intermediates, especially in the synthesis of natural products and their analogues.     

7‐Amino‐2‐methylsulfanyl‐1,2,4‐triazolo[1,5‐a]pyrimidine‐6‐carboxylic acid as the dimethylformamide and water monosolvates at 293 K

The molecular structure of 7‐amino‐2‐methylsulfanyl‐1,2,4‐triazolo[1,5‐a]pyrimidine‐6‐carboxylic acid is reported in two crystal environments, viz. as the dimethylformamide (DMF) monosolvate, C₇H₇N₅O₂S·C₃H₇NO, (I), and as the monohydrate, C₇H₇N₅O₂S·H₂O, (II), both at 293 (2) K. The triazolo[1,5‐a]pyrimidine molecule is of interest with respect to the possible biological activity of its coordination compounds. While the DMF solvate exhibits a layered structural arrangement through N...O hydrogen‐bonding interactions, the monohydrate displays a network of intermolecular O...O and N...O hydrogen bonds assisted by cocrystallized water molecules and weak π–π stacking interactions, leading to a different three‐dimensional supramolecular architecture. Based on results from topological analyses of the electron‐density distribution in X—H...O (X = O, N and C) regions, hydrogen‐bonding energies have been estimated from structural information only, enabling the characterization of hydrogen‐bond graph energies.     

Synthesis and structure characterization of new [1,2,4]triazolo[5,4‐d][1,5]benzothiazepine derivatives through 1,3‐dipolar cycloaddition reaction

Reaction of 1,5‐benzothiazepines 3 , obtained from chalcones 2 and o‐aminobenzenthiol, with the (phenylhydrazino) chloromethylenecarboxylates 4 in the presence of Et₃N leads to a series of new [1,2,4]triazolo[5,4‐d][1,5]benzothiazepine derivatives 5 . Their structures were established using spectroscopic methods and that of compound 5d was confirmed using X‐ray diffraction analysis. J. Heterocyclic Chem., (2011).